A new and improved strategy combining a dispersive-solid phase extraction-based multiclass method with ultra high pressure liquid chromatography for analysis of low molecular weight polyphenols in vegetables

This paper reports on the development and optimization of a modified Quick, Easy, Cheap Effective, Rugged and Safe (QuEChERS) based extraction technique coupled with a clean-up dispersive-solid phase extraction (dSPE) as a new, reliable and powerful strategy to enhance the extraction efficiency of free low molecular-weight polyphenols in selected species of dietary vegetables. The process involves two simple steps. First, the homogenized samples are extracted and partitioned using an organic solvent and salt solution. Then, the supernatant is further extracted and cleaned using a dSPE technique. Final clear extracts of vegetables were concentrated under vacuum to near dryness and taken up into initial mobile phase (0.1% formic acid and 20% methanol). The separation and quantification of free low molecular weight polyphenols from the vegetable extracts was achieved by ultrahigh pressure liquid chromatography (UHPLC) equipped with a phodiode array (PDA) detection system and a Trifunctional High Strength Silica capillary analytical column (HSS T3), specially designed for polar compounds. The performance of the method was assessed by studying the selectivity, linear dynamic range, the limit of detection (LOD) and limit of quantification (LOQ), precision, trueness, and matrix effects. The validation parameters of the method showed satisfactory figures of merit. Good linearity (View the MathML sourceRvalues2>0.954; (+)-catechin in carrot samples) was achieved at the studied concentration range. Reproducibility was better than 3%. Consistent recoveries of polyphenols ranging from 78.4 to 99.9% were observed when all target vegetable samples were spiked at two concentration levels, with relative standard deviations (RSDs, n = 5) lower than 2.9%. The LODs and the LOQs ranged from 0.005 μg mL−1 (trans-resveratrol, carrot) to 0.62 μg mL−1 (syringic acid, garlic) and from 0.016 μg mL−1 (trans-resveratrol, carrot) to 0.87 μg mL−1 ((+)-catechin, carrot) depending on the compound. The method was applied for studying the occurrence of free low molecular weight polyphenols in eight selected dietary vegetables (broccoli, tomato, carrot, garlic, onion, red pepper, green pepper and beetroot), providing a valuable and promising tool for food quality evaluation.

Potentialities of two solventless extraction approaches—Stir bar sorptive extraction and headspace solid-phase microextraction for determination of higher alcohol acetates, isoamyl esters and ethyl esters in wines

A stir bar sorptive extraction with liquid desorption followed by large volume injection coupled to gas chromatography–quadrupole mass spectrometry (SBSE-LD/LVI-GC–qMS) was evaluated for the simultaneous determination of higher alcohol acetates (HAA), isoamyl esters (IsoE) and ethyl esters (EE) of fatty acids. The method performance was assessed and compared with other solventless technique, the solid-phase microextraction (SPME) in headspace mode (HS). For both techniques, influential experimental parameters were optimised to provide sensitive and robust methods. The SBSE-LD/LVI methodology was previously optimised in terms of extraction time, influence of ethanol in the matrix, liquid desorption (LD) conditions and instrumental settings. Higher extraction efficiency was obtained using 60 min of extraction time, 10% ethanol content, n-pentane as desorption solvent, 15 min for the back-extraction period, 10 mL min−1 for the solvent vent flow rate and 10 °C for the inlet temperature. For HS-SPME, the fibre coated with 50/30 μm divinylbenzene/carboxen/polydimethylsiloxane (DVB/CAR/PDMS) afforded highest extraction efficiency, providing the best sensitivity for the target volatiles, particularly when the samples were extracted at 25 °C for 60 min under continuous stirring in the presence of sodium chloride (10% (w/v)). Both methodologies showed good linearity over the concentration range tested, with correlation coefficients higher than 0.984 for HS-SPME and 0.982 for SBES-LD approach, for all analytes. A good reproducibility was attained and low detection limits were achieved using both SBSE-LD (0.03–28.96 μg L−1) and HS-SPME (0.02–20.29 μg L−1) methodologies. The quantification limits for SBSE-LD approach ranging from 0.11 to 96.56 μg L−and from 0.06 to 67.63 μg L−1 for HS-SPME. Using the HS-SPME approach an average recovery of about 70% was obtained whilst by using SBSE-LD obtained average recovery were close to 80%. The analytical and procedural advantages and disadvantages of these two methods have been compared. Both analytical methods were used to determine the HAA, IsoE and EE fatty acids content in “Terras Madeirenses” table wines. A total of 16 esters were identified and quantified from the wine extracts by HS-SPME whereas by SBSE-LD technique were found 25 esters which include 2 higher alcohol acetates, 4 isoamyl esters and 19 ethyl esters of fatty acids. Generally SBSE-LD provided higher sensitivity with decreased analysis time.

Real-Time Visual SLAM Using Pre - Existing Floor Lines as Landmarks and a Single Camera

SANTANA, André M.; SANTIAGO, Gutemberg S.; MEDEIROS, Adelardo A. D. Real-Time Visual SLAM Using Pre-Existing Floor Lines as Landmarks and a Single Camera. In: CONGRESSO BRASILEIRO DE AUTOMÁTICA, 2008, Juiz de Fora, MG. Anais... Juiz de Fora: CBA, 2008.

Development of a new analytical approach based on cellulose membrane and chelator for differentiation of labile and inert metal species in aquatic systems

A new procedure was developed in this study, based on a system equipped with a cellulose membrane and a tetraethylenepentamine hexaacetate chelator (MD-TEPHA) for in situ characterization of the lability of metal species in aquatic systems. To this end, the DM-TEPHA system was prepared by adding TEPHA chelator to cellulose bags pre-purified with 1.0 mol L-1 of HCl and NaOH solutions. After the MD-TEPHA system was sealed, it was examined in the laboratory to evaluate the influence of complexation time (0-24 h), pH (3.0, 4.0, 5.0, 6.0 and 7.0), metal ions (Cu, Cd, Fe, Mn and Ni) and concentration of organic matter (15, 30 and 60 mg L-1) on the relative lability of metal species by TEPHA chelator. The results showed that Fe and Cu metals were complexed more slowly by TEPHA chelator in the MD-TEPHA system than were Cd, Ni and Mn in all pH used. It was also found that the pH strongly influences the process of metal complexation by the MD-TEPHA system. At all the pH levels, Cd, Mn and Ni showed greater complexation with TEPHA chelator (recovery of about 95-75%) than did Cu and Fe metals. Time also affects the lability of metal species complexed by aquatic humic substances (AHS); while Cd, Ni and Mn showed a faster kinetics, reaching equilibrium after about 100 min, and Cu and Fe approached equilibrium after 400 min. Increasing the AHS concentration decreases the lability of metal species by shifting the equilibrium to AHS-metal complexes. Our results indicate that the system under study offers an interesting alternative that can be applied to in situ experiments for differentiation of labile and inert metal species in aquatic systems. (c) 2006 Elsevier B.V. All rights reserved.

Analytical Methods for the Determination of Chlorhexidine: A Review

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Multivariate optimization and validation of an analytical methodology by RP-HPLC for the determination of losartan potassium in capsules

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Methacycline: A Review of Analytical Methods

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Development and validation of an analytical method by RP-HPLC for quantification of sibutramine hydrochloride in pharmaceutical capsules

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Correlations Between Pre- and Post-Fasting Growth in Nile Tilapia

We tested the correlation between growth rate before and after a food deprivation phase in twelve single held Nile tilapias, Oreochromis niloticus. The experiment was divided into three phases: before food deprivation (phase 1: 15 d), food deprivation (phase 2: 12 d) and refeeding (phase 3: 15 d). The specific growth rate - SGR, food conversion efficiency - FCE and feed ingestion increased significantly during phase 3. Positive and significant correlations were found either to SGR or to feed ingestion between Phase 1 and 3 but not for FCE. The SGR on phase 3, moreover, were positively correlated to FCE and feed ingestion, while on phase 1 SGR was positively correlated to FCE only. Thus, high pre-fasting SGR or feed ingestion reflects in likewise high post-fasting SGR or feed ingestion values. Moreover, since SGR and FCE are correlated to each other in both phase 1 and 3, but phase 3 SGR is also correlated to feed ingestion; we could suppose that hyperphagic behaviour could be the main compensatory mechanism. Accordingly, we suggest that a fish with an elevated growth performance shall display a proportionally raised post-fasting growth response in order to normalize its predetermined growth trajectory and resume its normal growth rate.

New analytical procedure based on a cellulose bag and ionic exchanger with p-aminobenzoic acid groups for differentiation of labile and inert metal species in aquatic systems

A new procedure was developed for the in situ characterization of the lability of metal species in aquatic systems by using a system equipped with a diffusion membrane and cellulose organomodified with p-aminobenzoic acid groups (DM-Cell-PAB). To this end, the DM-Cell-PAB system was prepared by adding cellulose organomodified with p-aminobenzoic acid groups (Cell-PAB) to pre-purified cellulose bags. After the DM-Cell-PAB system was sealed, it was examined in the laboratory to evaluate the influence of complexation time, mass of exchanger, pH, metal ions (Cu, Cd, Fe, Mn, and Ni), and concentration of organic matter on the relative lability of metal species. It was found that the pH and kinetics strongly influence the process of metal complexation by the DM-Cell-PAB system. At all pH levels, Cd, Mn, and Ni showed lower complexation with Cell-PAB resin than Cu and Fe metals. Note that relative lability of metals complexed to aquatic humic substances (AHS) in the presence of Cell-PAB resin showed the following order: Cu congruent to Fe >> Ni > Mn=Cd. The results presented here also indicate that increasing the AHS concentration decreases the lability of metal species by shifting the equilibrium to AHS-metal complexes. Our results indicate that the system under study offers an interesting alternative that can be applied to in situ experiments for differentiation of labile and inert metal species in aquatic systems.

Dominance and Subordination Interactions Among Nestmates in Pre and Post-Emergence Phases of the Basal Eusocial Wasp Mischocyttarus (Monogynoecus) montei (Hymenoptera, Vespidae)

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Sources of errors in the quantitative analysis of food carotenoids by HPLC

Several factors render carotenoid determination inherently difficult. Thus, in spite of advances in analytical instrumentation, discrepancies in quantitative results on carotenoids can be encountered in the international literature. A good part of the errors comes from the pre-chromatographic steps such as sampling scheme that does not yield samples representative of the food lots under investigation; sample preparation which does not maintain representativity and guarantee homogeneity of the analytical sample; incomplete extraction; physical losses of carotenoids during the various steps, especially during partition or washing and by adsorption to glass walls of containers; isomerization and oxidation of carotenoids during analysis. on the otherhand, although currently considered the method of choice for carotenoids, high performance liquid chromatography (HPLC) is subject to various sources of errors, such as: incompatibility of the injection solvent and the mobile phase, resulting in distorted or split peaks; erroneous identification; unavailability, impurity and instability of carotenoid standards; quantification of highly overlapping peaks; low recovery from the HPLC column; errors in the preparation of standard solutions and in the calibration procedure; calculation errors. Illustrations of the possible errors in the quantification of carotenoids by HPLC are presented.

Phase diagrams of a CTAB/organic solvent/buffer system applied to extraction of enzymes by reverse micelles

A partial pseudo-ternary phase diagram has been studied for the cethyltrimethylammonium bromide/isooctane:hexanol:butanol/potassium phosphate buffer system, where the two-phase diagram consisting of the reverse micelle phase (L-2) in equilibrium with the solvent is indicated. Based on these diagrams two-phase systems of reverse micelles were prepared with different compositions of the compounds and used for extraction and recovery of two enzymes, and the percentage of enzyme recovery yield monitored. The enzymes glucose-6-phosphate dehydrogenase (G6PD) and xylose redutase (XR) obtained from Candida guilliermondii yeast were used in the extraction procedures. The recovery yield data indicate that micelles having different composition give selective extraction of enzymes. The method can thus be used to optimize enzyme extraction processes. (c) 2007 Elsevier B.V. All rights reserved.

Thermotropic phase behavior in aqueous mixtures of dioctadecyldimethylammonium bromide and alkyltrimethylammonium bromide surfactant series studied by differential scanning calorimetry

The effect of the micelle-forming surfactant series alkyltrimethylammonium bromide (C(n)TAB, n = 12, 14, 16 and 18) on the thermotropic phase behavior of dioctadecyldimethylammonium bromide (DODAB) vesicles in water was investigated by differential scanning calorimetry at constant 5.0 mM total surfactant concentration and varying individual surfactant concentrations. The pre-, post- and main transition temperatures (T-s, T-p and T-m), melting enthalpy (Delta H) and peak width of the main transition (Delta T-1/2) are reported as a function of the surfactant molar fraction. No clear dependence of these parameters on the C(n)TAB chain length was found. At 5 mM, neat DODAB in water exhibits two transition temperatures, T-s = 32.1 and T-m = 42.7 degrees C, as obtained from the DSC upscans, but not a clear T-p. For every n, except n = 12, T-s vanishes as CnTAB concentration increases and approaches CMC. T-m behaves differently for different n, the longer C(14)TAB and C(16)TAB decrease, while C(18)TAB increases T-m with increasing concentration. The data indicate that changes in T-m, T-s, T-p and Delta H of the transition are related not only to the extent of C(n)TAB affinity to DODAB but also to the surfactant chain length. Accordingly, C18TAB yields a more compact bilayer, thus increasing T-m, while C(14)TAB and C(1G)TAB yield a less organized bilayer and reduce T-m. C(12)TAB does not much affect T-s and T-m, although it yields T-p approximate to 51.6 degrees C. (C) 2008 Elsevier B.V. All rights reserved.

The role of counterion on the thermotropic phase behavior of DODAB and DODAC vesicles

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)